WO1996011907A1 - Enhanced solubilization of zinc and manganese methionine complex salts by addition of ferric ion - Google Patents
Enhanced solubilization of zinc and manganese methionine complex salts by addition of ferric ion Download PDFInfo
- Publication number
- WO1996011907A1 WO1996011907A1 PCT/US1995/013222 US9513222W WO9611907A1 WO 1996011907 A1 WO1996011907 A1 WO 1996011907A1 US 9513222 W US9513222 W US 9513222W WO 9611907 A1 WO9611907 A1 WO 9611907A1
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- WO
- WIPO (PCT)
- Prior art keywords
- zinc
- methionine
- manganese
- ferric ion
- ferric
- Prior art date
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000011701 zinc Substances 0.000 title claims abstract description 26
- 150000003839 salts Chemical class 0.000 title claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 24
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001447 ferric ion Inorganic materials 0.000 title claims abstract description 15
- BZVFZBYIWNIHHL-WCCKRBBISA-N (2s)-2-amino-4-methylsulfanylbutanoic acid;manganese Chemical compound [Mn].CSCC[C@H](N)C(O)=O BZVFZBYIWNIHHL-WCCKRBBISA-N 0.000 title abstract description 6
- 230000007928 solubilization Effects 0.000 title description 4
- 238000005063 solubilization Methods 0.000 title description 4
- 229930182817 methionine Natural products 0.000 claims abstract description 25
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000011572 manganese Substances 0.000 claims abstract description 14
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002696 manganese Chemical class 0.000 claims abstract description 5
- 230000002708 enhancing effect Effects 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 150000002739 metals Chemical class 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 235000006109 methionine Nutrition 0.000 description 22
- CNMFGFBWPBBGKX-SCGRZTRASA-L zinc;(2s)-2-amino-4-methylsulfanylbutanoate Chemical class [Zn+2].CSCC[C@H](N)C([O-])=O.CSCC[C@H](N)C([O-])=O CNMFGFBWPBBGKX-SCGRZTRASA-L 0.000 description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 7
- 229940032296 ferric chloride Drugs 0.000 description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229940110280 zinc methionine Drugs 0.000 description 7
- -1 MANGANESE ALPHA AMINO ACID Chemical class 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 235000008206 alpha-amino acids Nutrition 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 150000003751 zinc Chemical class 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- 239000004472 Lysine Substances 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 241000605112 Scapanulus oweni Species 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002742 methionines Chemical class 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 239000004470 DL Methionine Substances 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 150000001370 alpha-amino acid derivatives Chemical class 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- 239000003797 essential amino acid Substances 0.000 description 1
- 239000006052 feed supplement Substances 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 229940032950 ferric sulfate Drugs 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical compound CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/57—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
- C07C323/58—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
Definitions
- This invention relates to an improvement in the properties of dry powder complexes of zinc and manganese with methionine in the 1:1 ratio. In that sense it represents a significant improvement over the process disclosed in commonly owned U.S. Patent 4,764,633, and as well, over commonly owned and now expired U.S. Patent 3,941,818 issued March 2, 1976 entitled “1:1 ZINC METHIONINE COMPLEXES", and United States Letters Patent 3,950,372 issued April 13, 1976, and entitled “1:1 MANGANESE ALPHA AMINO ACID COMPLEXES”.
- patent 3,941,818 and U.S. Patent 3,950,372 relate to 1:1 complexed salts per se of zinc and manganese with the amino acid methionine. These salts, as identified in the earlier patents, have the useful feature of being highly body absorbable nutritional supplements for animals that provide readily available sources of zinc and manganese on the one hand, and the essential amino acid methionine on the other.
- Complexes of lysine are very easily soluble in water. However, complexes of metals such as zinc and manganese and methionine are less soluble in water than the complexes of metals and lysine.
- the supplement For effective feed supplements, the supplement must be in a powdered, dry form, and it must be readily soluble in the gut of animals; otherwise, much of the supplement will not be absorbed into the blood stream. It also is useful to have water soluble supplements so that the user may administer them through aqueous systems.
- This invention has as its primary objective the fulfillment of this need in order that dry 1:1 manganese methionine complexes and dry 1:1 zinc methionine complexes have enhanced solubility in comparison with those prepared as described in U.S. Patent 3,941,818 and U.S. Patent 3,950,372.
- complexed salts are referred to as complexed salts.
- These salts are to be carefully distinguished from conventional salts such as, for example, zinc chloride or manganese chloride.
- Such conventional salts such as zinc chloride or manganese chloride contain only an electrostatic attraction between the cation and the anion.
- the 1:1 complexed salts prepared by this invention differ from conventional salts in that while they have an electrostatic attraction between the cation and the anion, there is also a coordination bond between the cation and the amino moiety of the alpha amino acid.
- manganese alpha amino acid complex salts of the present invention they have the formula:
- the process of preparing the desired zinc and methionine 1:1 complex salts of methionine as referred to herein is straightforward and direct. Commonly it begins with the use of a water soluble zinc salt and/or a water soluble manganese salt, respectively.
- Suitable zinc salts which can be employed are the halides, the sulfates, and the phosphates. The desired molar ratio of zinc salt to methionine is 1:1.
- Suitable manganese salts which can be employed are likewise halides, sulfates and phosphates. The desired molar ratio of manganese to methionine is 1:1. In each instance, the sulfate salts are preferred from the standpoint of availability and, at least currently, cost.
- these salts are at least partially water dissolved, preferably at elevated temperatures. Temperatures within the range of from about 180 ⁇ F to about 205 ⁇ F have been found desirable, most preferably temperatures within the range of 190 ⁇ F to about 205 ⁇ F. In actual practice, one common technique is to stir the salt into a water solution while simultaneously injecting steam to elevate the temperature within the desired range.
- the amount of dry weight molar basis based upon the mole weight of zinc or manganese should be from about 15% to about 30% on a mole weight basis. Preferably the amount is within the range of from 15% to 20%. As evidenced by the examples, the amount appears to be critical in order to achieve the desired solubility of the dry weight product. In other words, the enhanced solubility phenomena of the present invention is not achieved until the level of ferric ion salt added is at least 15%. Thus the levels expressed in U.S. Patent 4,764,633 are too low to provide the observed enhanced solubility phenomena of the present invention.
- the ferric ion which is added may be in the form of any water soluble salt such as ferric chloride, ferric sulfate, ferric phosphate, ferric acitate, or any other suitable water soluble ferric salt.
- ferric chloride was found to enhance the solubility of zinc methionine acid sulfate.
- concentration of ferric chloride required to produce a readily soluble and stable material is critical. The following experiment was conducted to determine the optimum concentration of ferric chloride.
- Zinc sulfate heptahydrate (ZnSOg.7H 0; 14.38g; 0.05 mole) was dissolved in 30 mL of distilled water in a 250 mL beaker.
- DL-Methionine (7.46g, 0.05 mole) was added. The mixture was heated to boiling, and the heating continued for an additional 10 minutes.
- Ferric chloride hexahydrate (Fecl3-6H 0, 13.52 g ; 0.05 mole) was transferred into a 100 mL volumetric flask. The solid was dissolved in approximately 50 mL of H 0. Water was added to volume.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Method of enhancing the water solubility of dry zinc and/or manganese methionine complex salts by reacting a water soluble zinc and/or manganese salt with methionine in the presence of ferric ion with the amount being between at least 15 mole percent of the amount of zinc and/or manganese present.
Description
ENHaANCED SOLUBILIZATION OF ZINC AND MANGANESE METHIONINE COMPLEX SALTS BY ADDITION OF FERRIC ION
BACKGROUND OF THE INVENTION
This invention relates to an improvement in the properties of dry powder complexes of zinc and manganese with methionine in the 1:1 ratio. In that sense it represents a significant improvement over the process disclosed in commonly owned U.S. Patent 4,764,633, and as well, over commonly owned and now expired U.S. Patent 3,941,818 issued March 2, 1976 entitled "1:1 ZINC METHIONINE COMPLEXES", and United States Letters Patent 3,950,372 issued April 13, 1976, and entitled "1:1 MANGANESE ALPHA AMINO ACID COMPLEXES". Thus patent 3,941,818 and U.S. Patent 3,950,372 relate to 1:1 complexed salts per se of zinc and manganese with the amino acid methionine. These salts, as identified in the earlier patents, have the useful feature of being highly body absorbable nutritional supplements for animals that provide readily available sources of zinc and manganese on the one hand, and the essential amino acid methionine on the other.
The common assignee of both of these patents makes a variety of transition metal complexes with alpha amino acids for sale. For example, see U.S. Patent 5,061,815 relating to metal lysine complexes and methods for producing metal lysine complexes, as well as U.S. Patent 5,278,329 for L-form 1:1 metal methionine complexes.
Complexes of lysine are very easily soluble in water. However, complexes of metals such as zinc and manganese and methionine are less soluble in water than the complexes of metals and lysine.
In Anderson, U.S. Patent 4,764,633, an improvement in the complexing process is disclosed wherein the complexing of either zinc or manganese ions with methionine is conducted in
the presence of a catalytically effective amount of ferric ion. The amount of ferric ion described is about 2% to about 10% based on the dry weight basis of the methionine, preferably from about 4% to about 8% based on the dry weight basis of the methionine.
For effective feed supplements, the supplement must be in a powdered, dry form, and it must be readily soluble in the gut of animals; otherwise, much of the supplement will not be absorbed into the blood stream. It also is useful to have water soluble supplements so that the user may administer them through aqueous systems.
While U.S. Patent 4,764,633 enhances the amount of complexation, it does not enhance the solubility of the final dry product.
Accordingly, there has been a real and a continuing need for the discovery of a process which will enhance the solubility characteristics of the dry 1:1 complexes of zinc and manganese with methionine.
This invention has as its primary objective the fulfillment of this need in order that dry 1:1 manganese methionine complexes and dry 1:1 zinc methionine complexes have enhanced solubility in comparison with those prepared as described in U.S. Patent 3,941,818 and U.S. Patent 3,950,372.
For details of the desirability and the utility of 1:1 manganese methionine complexes, see the previously referred to U.S. Patent 3,950,372 which is incorporated herein by reference. For details of the desirability and the utility of 1:1 zinc methionine complexes, see U.S. Patent No. 3,941,818, which is incorporated herein by reference.
The method of accomplishing each of the above objectives of this invention will become apparent from the detailed description of the invention which follows hereinafter.
SUMMARY OF THE INVENTION
Method of enhancing the water solubility of dry zinc methionine complex salts by reacting in water soluble zinc salt with methionine in the presence of ferric ion with the
amount being between 15 mole percent and 30 mole percent of the amount of zinc present.
DETAILED DESCRIPTION OF THE INVENTION
It is important to note that the respective zinc and manganese compounds which are prepared in accordance with this invention are referred to as complexed salts. These salts are to be carefully distinguished from conventional salts such as, for example, zinc chloride or manganese chloride. Such conventional salts such as zinc chloride or manganese chloride contain only an electrostatic attraction between the cation and the anion. The 1:1 complexed salts prepared by this invention differ from conventional salts in that while they have an electrostatic attraction between the cation and the anion, there is also a coordination bond between the cation and the amino moiety of the alpha amino acid.
With regard to the zinc methionine complexed salts which are prepared in accordance with the improved process of this invention, they have the general formula:
wherein X is an anion and w is an integer equal to the anionic charge of X. The cation of these complexed salts is represented by the bracketed material in the above formula and represents a 1:1 complex of zinc and methionine.
With regard to the manganese alpha amino acid complex salts of the present invention, they have the formula:
CH3-S-CH2-CH2-CH-C-0-Mn
- NH2 _l w
X and w are as previously defined.
The process of preparing the desired zinc and methionine 1:1 complex salts of methionine as referred to herein is straightforward and direct. Commonly it begins with the use of a water soluble zinc salt and/or a water soluble manganese salt, respectively. Suitable zinc salts which can be employed are the halides, the sulfates, and the phosphates. The desired molar ratio of zinc salt to methionine is 1:1. Suitable manganese salts which can be employed are likewise halides, sulfates and phosphates. The desired molar ratio of manganese to methionine is 1:1. In each instance, the sulfate salts are preferred from the standpoint of availability and, at least currently, cost.
In the general process, these salts are at least partially water dissolved, preferably at elevated temperatures. Temperatures within the range of from about 180βF to about 205βF have been found desirable, most preferably temperatures within the range of 190βF to about 205βF. In actual practice, one common technique is to stir the salt into a water solution while simultaneously injecting steam to elevate the temperature within the desired range.
In accordance with the process of our prior patent, U.S. Patent 4,764,633, along with these reactants, a catalytically effective amount of ferric ion is added to enhance complexation yield. The amount added is from about 2% to about 10% based upon the dry weight of methionine. The earlier patent teaches that levels above the 10 molar percent level based upon the dry weight of methionine should be avoided. This corresponds to the same molar percentages for zinc, i.e. 2% to 10%, and preferably 4% to 8%. As previously mentioned in the earlier patent, it was discovered that when percentages of ferric ion are added to the reactants at the levels there specified, desirable things occur. In the first instance, the dissolving of the salt and the amino acid in the water appears to be significantly enhanced, and in the second instance there is an increased yield of the desirable
1:1 complexes formed. That earlier discovery, however, involved formation of the reactants and did not involve solving the problems that zinc and manganese methionine complexes are inherently difficultly soluble at best after formation.
It has now been surprisingly discovered that if substantially increased amounts of ferric ion are added during the formation reaction for the complexes, not only does one get a substantially increased yield of the desirable 1: 1 complexes, but in addition the dry product produced by the process is more soluble, and the solution produced is more stable.
For purposes of this invention, the amount of dry weight molar basis based upon the mole weight of zinc or manganese should be from about 15% to about 30% on a mole weight basis. Preferably the amount is within the range of from 15% to 20%. As evidenced by the examples, the amount appears to be critical in order to achieve the desired solubility of the dry weight product. In other words, the enhanced solubility phenomena of the present invention is not achieved until the level of ferric ion salt added is at least 15%. Thus the levels expressed in U.S. Patent 4,764,633 are too low to provide the observed enhanced solubility phenomena of the present invention.
While not wishing to be bound by any theory of operability, it is believed that the presence of the ferric ion, along with the manganese or the zinc ion and methionine, brings about an equilibrium between ferric methionine complexes and those of zinc and manganese. Since the ferric ion complexes formed are much more soluble than either the zinc or the manganese complexes, the equilibrium that occurs seems to shift the equilibrium in the reaction of the zinc and the methionine to provide a far more soluble product. In any event, the important fact is not theoretically how the reaction works, but that it does simply work to provide a product of significantly enhanced solubility.
The ferric ion which is added may be in the form of any water soluble salt such as ferric chloride, ferric sulfate, ferric phosphate, ferric acitate, or any other suitable water soluble ferric salt. The most preferred, however, is ferric chloride and ferric sulfate.
The following examples are offered to further illustrate the improved process of the present invention and the critical levels of ferric ion required to achieve the enhanced solubility of the dry products prepared.
EXAMPLES OF ZINC METHIONINE ACID SULFATE SOLUBILIZATION BY
FERRIC CHLORIDE
The addition of ferric chloride was found to enhance the solubility of zinc methionine acid sulfate. However, the concentration of ferric chloride required to produce a readily soluble and stable material is critical. The following experiment was conducted to determine the optimum concentration of ferric chloride.
Seven samples of zinc methionine acid sulfate containing variable concentrations of Fecl3 were prepared. Zinc sulfate heptahydrate (ZnSOg.7H 0; 14.38g; 0.05 mole) was dissolved in 30 mL of distilled water in a 250 mL beaker. DL-Methionine (7.46g, 0.05 mole) was added. The mixture was heated to boiling, and the heating continued for an additional 10 minutes.
Ferric chloride hexahydrate (Fecl3-6H 0, 13.52g; 0.05 mole) was transferred into a 100 mL volumetric flask. The solid was dissolved in approximately 50 mL of H 0. Water was added to volume.
Using a 50 mL burret, a specific volume of the ferric chloride solution was added to each of the boiling solutions of zinc methionine acid sulfate (Table 1). Each solution was evaporated to dryness under reduced pressure at 70CC using a rotary evaporator. A sample (1.0g) of each of the dried products was transferred into a stoppered test tube. Distilled water was added in 0.5 mL increments and thoroughly
mixed. The volume required for complete solubilization of the sample is reported in Table 2.
TABLE 1
Sample Zinc Sulfate DL- Ferric Ferric Fe/Zn mole %
No. wt.g. mole Methionine Chloride Chloride wt.g. mole Solution mole (mL)
1 14.3% 0.05 7.46 0.05 5 0.0025 5
2 14.3% 0.05 7.46 0.05 7 0.0035 7
3 14.3% 0.05 7.46 0.05 9 0.0045 9
4 14.3% 0.05 7.46 0.05 11 0.0055 11
5 14.3% 0.05 7.46 0.05 13 0.0065 13
6 14.3% 0.05 7.46 0.05 15 0.0075 15
7 14.3% 0.05 7.46 0.05 17 0.0085 17
TABLE 2
Fe/Zn Feel3/Methionine Vol. of Hater Solubility
Molar % w/w% to Dissolve ig g/BL
Sample (mL)
1 5 5.44 12.5 0.08*
2 7 7.62 12.5 0.08*
3 9 9.80 11.0 0.09*
4 11 11.97 10.5 0.10*
5 13 14.15 9.5 0.11*
6 15 16.33 2.5 0.40
7 17 18.51 2.0 0.50
♦Solution was unstable, A white ppt of Methionine was formed upon standing.
From the above Table 1 and Table 2 it can be seen that a critical limit occurs with the demarcation line between 13 molar percent and 15 molar percent. In practice with other experiments (not specifically shown here), it seems that only a little increased value is obtained in going beyond 15%. In other words, the increased solubility does not significantly improve, even though the level might go up to as much as 30%. Thus, at least 15% appears to be the critical distinction and 30% is a practical and economic upper limit.
Claims
1. A method of enhancing the water solubility of dry methionine complex salts of the metals zinc and/or manganese, said method comprising: reacting a water soluble metal salt with the metal being selected from the group consisting of zinc and manganese salts with methionine in the presence of ferric ion, the amount of ferric ion being at least 15 molar percent of the amount of metal salt present.
2. The process of claim 1 wherein the metal is zinc.
3. The process of claim 1 wherein the metal is manganese.
4. The process of claim 1 wherein the amount of ferric ion is within the range of 15 molar percent to 30 molar percent of the amount of metal salt present.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK95939517T DK0787125T3 (en) | 1994-10-18 | 1995-10-16 | Improved solubilization of zinc and manganese-methionine complex salts by addition of ferric ion |
| AU41304/96A AU686914B2 (en) | 1994-10-18 | 1995-10-16 | Enhanced solubilization of zinc and manganese methionine complex salts by addition of ferric ion |
| EP95939517A EP0787125B1 (en) | 1994-10-18 | 1995-10-16 | Enhanced solubilization of zinc and manganese methionine complex salts by addition of ferric ion |
| JP8513396A JP2899992B2 (en) | 1994-10-18 | 1995-10-16 | Improvement of solubility of zinc methionine complex and manganese methionine complex by addition of ferric ion |
| NZ296645A NZ296645A (en) | 1994-10-18 | 1995-10-16 | Enhanced solubilisation of zinc and manganese methionine complex salts by addition of ferric ion |
| DE69506903T DE69506903T2 (en) | 1994-10-18 | 1995-10-16 | INCREASED SOLUBILIZATION OF COMPLEX SALTS OF METHIONINE WITH ZINC AND MANGANE BY THE ADDITION OF FERRIIONS |
| CA 2202145 CA2202145C (en) | 1994-10-18 | 1995-10-16 | Enhanced solubilization of zinc and manganese methionine complex salts by addition of ferric ion |
| KR1019970702542A KR100218976B1 (en) | 1994-10-18 | 1995-10-16 | Enhanced solubilization of zinc and manganese methionine complex salts by addition of ferric ion |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/324,881 US5430164A (en) | 1994-10-18 | 1994-10-18 | Enhanced solubilization of zinc and manganese methionine complex salts by addition of ferric ion |
| US08/324,881 | 1994-10-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1996011907A1 true WO1996011907A1 (en) | 1996-04-25 |
Family
ID=23265504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1995/013222 WO1996011907A1 (en) | 1994-10-18 | 1995-10-16 | Enhanced solubilization of zinc and manganese methionine complex salts by addition of ferric ion |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5430164A (en) |
| EP (1) | EP0787125B1 (en) |
| JP (1) | JP2899992B2 (en) |
| KR (1) | KR100218976B1 (en) |
| AT (1) | ATE174906T1 (en) |
| AU (1) | AU686914B2 (en) |
| DE (1) | DE69506903T2 (en) |
| DK (1) | DK0787125T3 (en) |
| ES (1) | ES2127574T3 (en) |
| NZ (1) | NZ296645A (en) |
| WO (1) | WO1996011907A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010098632A3 (en) * | 2009-02-27 | 2011-04-07 | 씨제이제일제당 주식회사 | Method for increasing the solubility of methionine by mineral addition and acid treatment |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6767741B1 (en) * | 1999-08-27 | 2004-07-27 | Invitrogen Corporation | Metal binding compounds and their use in cell culture medium compositions |
| US6166071A (en) * | 2000-03-13 | 2000-12-26 | Albion International, Inc. | Zinc amino acid chelates having ligands comprised of glycine and a sulfur-containing amino acids |
| KR100458132B1 (en) * | 2002-03-22 | 2004-11-18 | 프로켐주식회사 | Method for preparing dried powder of metal-amino acid complex |
| US7247328B2 (en) * | 2002-05-31 | 2007-07-24 | Zinpro Corporation | Chromium (III) alpha amino acid complexes |
| US7129375B2 (en) * | 2002-10-16 | 2006-10-31 | Zinpro Corporation | Metal complexes of α amino dicarboxylic acids |
| KR100481326B1 (en) * | 2004-06-22 | 2005-04-07 | 주식회사 동암비티 | Producing process for organic chelate |
| CN110143899A (en) * | 2019-06-12 | 2019-08-20 | 禄丰天宝磷化工有限公司 | Clean and environment-friendly production method and device of methionine complex metal salt |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3463858A (en) * | 1965-05-06 | 1969-08-26 | Dean R Anderson | Organic zinc feed additive and method of making same |
| US3941818A (en) * | 1973-08-20 | 1976-03-02 | Zinpro Corporation | 1:1 Zinc methionine complexes |
| US4067994A (en) * | 1976-03-26 | 1978-01-10 | Zinpro Corporation | Iron methionine complex salts |
| US4764633A (en) * | 1987-08-31 | 1988-08-16 | Zinpro Corporation | Ferric ion catalyzed complexation of zinc and/or manganese with alpha amino acids |
| US5278329A (en) * | 1992-02-21 | 1994-01-11 | Zinpro Corporation | L-form 1:1 metal methionine complexes |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4039681A (en) * | 1973-08-20 | 1977-08-02 | Zinpro Corporation | Zinc methionine complex for acne treatment |
| US4021569A (en) * | 1973-08-20 | 1977-05-03 | Zinpro Corporation | Method of nutritional supplementation for zinc and methionine by ingesting 1:1 zinc methionine complexes |
| US3925433A (en) * | 1973-09-10 | 1975-12-09 | Zinpro Corp | 1:1 And 2:1 chromium, alpha amino acid complex salts |
| US3950372A (en) * | 1974-07-03 | 1976-04-13 | Zinpro Corporation | 1:1 Manganese alpha amino acid complexes |
| US4670269A (en) * | 1985-06-26 | 1987-06-02 | Zinpro Corporation | Cobalt complexes and their use as nutritional supplements |
| US4678854A (en) * | 1986-11-25 | 1987-07-07 | Zinpro Corporation | Cobalt complexes and their use as nutritional supplements |
| US5061815A (en) * | 1988-07-06 | 1991-10-29 | Zinpro Corporation | Metal lysine complexes and method for producing metal lysine complexes |
| US4956188A (en) * | 1988-10-20 | 1990-09-11 | Zinpro Corporation | Copper complexes with alpha hydroxy organic acids and their use as nutritional supplements |
| US4900561A (en) * | 1989-01-03 | 1990-02-13 | Zinpro Corporation | Copper complexes of alpha-amino acids that contain terminal amino groups, and their use as nutritional supplements |
| US4948594A (en) * | 1989-01-03 | 1990-08-14 | Zinpro Corporation | Copper complexes of alpha-amino acids that contain terminal amino groups, and their use as nutritional supplements |
-
1994
- 1994-10-18 US US08/324,881 patent/US5430164A/en not_active Expired - Lifetime
-
1995
- 1995-10-16 EP EP95939517A patent/EP0787125B1/en not_active Expired - Lifetime
- 1995-10-16 JP JP8513396A patent/JP2899992B2/en not_active Expired - Lifetime
- 1995-10-16 AT AT95939517T patent/ATE174906T1/en active
- 1995-10-16 AU AU41304/96A patent/AU686914B2/en not_active Expired
- 1995-10-16 DK DK95939517T patent/DK0787125T3/en active
- 1995-10-16 NZ NZ296645A patent/NZ296645A/en not_active IP Right Cessation
- 1995-10-16 DE DE69506903T patent/DE69506903T2/en not_active Expired - Lifetime
- 1995-10-16 ES ES95939517T patent/ES2127574T3/en not_active Expired - Lifetime
- 1995-10-16 WO PCT/US1995/013222 patent/WO1996011907A1/en active IP Right Grant
- 1995-10-16 KR KR1019970702542A patent/KR100218976B1/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3463858A (en) * | 1965-05-06 | 1969-08-26 | Dean R Anderson | Organic zinc feed additive and method of making same |
| US3941818A (en) * | 1973-08-20 | 1976-03-02 | Zinpro Corporation | 1:1 Zinc methionine complexes |
| US4067994A (en) * | 1976-03-26 | 1978-01-10 | Zinpro Corporation | Iron methionine complex salts |
| US4764633A (en) * | 1987-08-31 | 1988-08-16 | Zinpro Corporation | Ferric ion catalyzed complexation of zinc and/or manganese with alpha amino acids |
| US5278329A (en) * | 1992-02-21 | 1994-01-11 | Zinpro Corporation | L-form 1:1 metal methionine complexes |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010098632A3 (en) * | 2009-02-27 | 2011-04-07 | 씨제이제일제당 주식회사 | Method for increasing the solubility of methionine by mineral addition and acid treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| AU4130496A (en) | 1996-05-06 |
| DE69506903D1 (en) | 1999-02-04 |
| KR100218976B1 (en) | 1999-10-01 |
| JP2899992B2 (en) | 1999-06-02 |
| JPH10512545A (en) | 1998-12-02 |
| ATE174906T1 (en) | 1999-01-15 |
| KR970707086A (en) | 1997-12-01 |
| DK0787125T3 (en) | 1999-08-23 |
| NZ296645A (en) | 1998-01-26 |
| EP0787125A1 (en) | 1997-08-06 |
| DE69506903T2 (en) | 1999-06-10 |
| EP0787125B1 (en) | 1998-12-23 |
| US5430164A (en) | 1995-07-04 |
| AU686914B2 (en) | 1998-02-12 |
| ES2127574T3 (en) | 1999-04-16 |
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